A rare earth doped fluorescent glass for special yellow light illumination and its preparation method and application

Abstract

The present application belongs to the technical field of optical materials, and particularly relates to a rare earth doped fluorescent glass for special yellow light illumination and a preparation method and application thereof. The rare earth doped fluorescent glass comprises a glass matrix, rare earth fluorescent powder dispersed in the glass matrix, and a functional additive. The functional additive comprises rare earth oxides and scattering particles. The rare earth oxides are one or more of CeO2, Y2O3, Gd2O3, Nd2O3 and Eu2O3. The scattering particles are one or more of SiO2, Al2O3, ZrO2, TiO2 and VO2. The mass percentage of the glass matrix and the rare earth fluorescent powder is 70-90 wt%, the mass percentage of the glass matrix and the functional additive is 8-28 wt%, and the mass percentage of the rare earth fluorescent powder and the functional additive is 0.5-2 wt%. The rare earth ion fluorescent glass of the present application realizes high spectral purity output and effectively suppresses ultraviolet light and blue light components.

Description

Technical Field

[0001] This invention belongs to the field of optical materials technology, specifically relating to a rare earth-doped fluorescent glass for special yellow light illumination, its preparation method, and its application. Background Technology

[0002] In semiconductor manufacturing, precision optical inspection, and microelectronic packaging, yellow light illumination is widely used as a key auxiliary light source. Especially in photolithography and microstructure inspection processes, high spectral purity within the visible light range is required, with strict avoidance of ultraviolet and short-wavelength blue light components to prevent undesirable exposure or photo-induced damage to photosensitive materials. Therefore, developing a stable and efficient yellow light source capable of outputting no ultraviolet components is of great significance for improving process precision and ensuring product yield.

[0003] Current yellow light sources mainly rely on quantum dot films, organic encapsulation of inorganic phosphors, or traditional fluorescent glasses. However, these technologies all have certain shortcomings: quantum dot materials are prone to thermal quenching and photocatalytic degradation under high-power excitation, resulting in short lifetimes and poor spectral stability; organically encapsulated fluorescent films have insufficient temperature resistance, and are prone to yellowing, aging, and blue light leakage under long-term operation; the sintering temperature of traditional fluorescent glasses is relatively high, which can easily trigger reactions between the phosphor and the glass substrate, causing a decrease in luminous efficiency and spectral impurity. These problems limit the further promotion of existing yellow light sources in applications requiring high reliability and high spectral purity. Summary of the Invention

[0004] To address the problems existing in the prior art, the purpose of this invention is to design and provide a rare-earth-doped fluorescent glass for special yellow light illumination, comprising a glass matrix, rare-earth phosphors dispersed within the glass matrix, and functional additives: The functional additives include rare earth oxides and scattering particles, wherein the rare earth oxides are one or more of CeO2, Y2O3, Gd2O3, Nd2O3, and Eu2O3, and the scattering particles are one or more of SiO2, Al2O3, ZrO2, TiO2, and VO2. The glass matrix and rare earth phosphor have a mass percentage of 70–90 wt%, the glass matrix and functional additives have a mass percentage of 8–28 wt%, and the rare earth phosphors and functional additives have a mass percentage of 0.5–2 wt%.

[0005] Furthermore, the glass matrix comprises, by molar percentage, 50-60 mol% SiO2, 15-25 mol% B2O3, 5-12 mol% P2O5, 3-7 mol% Bi2-O3, 2-5 mol% ZnO, 2-4 mol% Al2O3, and 0.5-2 mol% SnF2.

[0006] Furthermore, the rare earth ion in the rare earth phosphor is La. 3+ Ce 3+ Eu 3+ 、Tb 3+ Gd 3+ 、Sm 3+ Pr 3+ At least one of them.

[0007] Furthermore, the particle size of the scattering particles is 50–300 nm.

[0008] Furthermore, the fluorescent glass can absorb ultraviolet and blue light with wavelengths of 200nm to 500nm, and emit light with wavelengths of 500nm to 700nm.

[0009] A second aspect of the present invention provides a method for preparing rare-earth-doped fluorescent glass as described above, comprising the following steps: S1: Mix glass matrix powder, rare earth phosphor, rare earth oxide and scattering particles, add dispersant and solvent, disperse by ball milling and dry to obtain dry powder or slurry; S2: The dry powder or slurry is loaded into a graphite or metal mold, and the inner wall of the mold is coated with a boron nitride or graphite paper isolation layer; S3: Densification is carried out in a spark plasma sintering apparatus by applying pulsed current and pressure of 20–60 MPa at 380–580 °C, and then cooling in a vacuum or inert atmosphere. S4: The resulting dense body is annealed at 200–500 °C and then ground and polished to obtain rare earth-doped fluorescent glass.

[0010] Further, the dispersant in step S1 is at least one of polyvinylpyrrolidone, polycarboxylate, polyacrylate or sodium dodecyl sulfate, and the solvent is at least one of ethanol, isopropanol, propylene glycol methyl ether or N-methylpyrrolidone.

[0011] Furthermore, in step S3, the heating rate is controlled at 5–50 ℃ / min, and the holding time is controlled at 2–15 min.

[0012] The third aspect of the present invention provides the application of the rare earth ion fluorescent glass as described above or the preparation method as described above in optical materials.

[0013] The present invention has the following beneficial effects: (1) The rare earth ion fluorescent glass of the present invention can achieve efficient spectral conversion of 500–700 nm yellow light under light source excitation, achieve high spectral purity output, and effectively suppress ultraviolet light and blue light components.

[0014] (2) The composite design of the glass components and functional additives described in this invention enables the glass to have strong ultraviolet absorption capacity, excellent thermal stability and anti-light decay performance, and improves the uniformity and comfort of lighting.

[0015] (3) The present invention adopts a low-temperature short-time densification process of spark plasma sintering, which can effectively maintain the structure and luminescence performance of rare earth phosphors and ensure uniform glass composition and tight interface bonding. Attached Figure Description

[0016] Figure 1 The emission spectrum of the rare-earth-doped fluorescent glass used for special yellow light illumination in Example 1 is shown under blue light excitation.

[0017] Figure 2 The light intensity spectra in the 380-520 nm range of the rare earth-doped fluorescent glass used for special yellow light illumination in Example 1 and Comparative Examples 1 and 2 are shown.

[0018] Figure 3 This is the CIE1931 chromaticity diagram of the rare-earth-doped fluorescent glass used for special yellow light illumination in Example 1. Detailed Implementation

[0019] The following specific embodiments illustrate the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and various details in this specification can be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention. It should be noted that, unless otherwise specified, the following embodiments and features can be combined with each other. Unless otherwise specified, the methods used in the embodiments of the present invention are conventional methods, and the reagents used are commercially available.

[0020] Example 1: A rare-earth-doped fluorescent glass for special yellow light illumination The fluorescent glass is composed of a glass matrix, rare earth phosphors, and functional additives. The composition of the glass matrix, by molar percentage, is: SiO2 55 mol%, B2O3 20 mol%, P2O5 8 mol%, Bi2O3 5 mol%, ZnO 5 mol%, Al2O3 5 mol%, SnF2 2 mol%. The total amount of the glass matrix added is 88.7%.

[0021] The rare earth phosphor is selected from Ce. 3+ Lu3Al5O doped 12 Phosphor and Eu 3+ The total amount of CaAlSiN3 phosphor added was 10 wt%.

[0022] The functional additives include 0.8 wt% CeO2 and 0.5 wt% nano-SiO2 particles, wherein CeO2 is used to enhance ultraviolet absorption and nano-SiO2 particles are used to enhance intra-sheet scattering and light field uniformity.

[0023] The preparation method of fluorescent glass is as follows: S1: Mix the above-mentioned raw materials, add 5 wt% ethanol solvent and 1 wt% polyvinylpyrrolidone dispersant, and obtain a uniform slurry by planetary ball milling for 2 h; obtain powder after low-temperature drying.

[0024] S2: Load the powder into a graphite mold, pre-coat the mold wall with a boron nitride isolation layer, level the powder layer, and set the graphite sheet electrode contact surface.

[0025] S3: In a spark plasma sintering apparatus, an initial pressure of 10 MPa is applied under vacuum, the temperature is increased to 500 ℃ at 50 ℃ / min, and held at 20 MPa pressure for 8 min to obtain a dense body.

[0026] S4: After annealing the obtained sintered body at 450 °C for 15 min, double-sided grinding and polishing were performed to obtain a sheet with a thickness of 0.5 mm and a surface roughness better than Ra 20 nm.

[0027] Testing with a blue LED excitation source revealed that the emission spectrum of this fluorescent glass was primarily distributed in the 500–700 nm range. No ultraviolet or blue light leakage below 500 nm was detected in the spectrum, verifying its high spectral purity and yellow light output characteristics. Figure 1 As shown.

[0028] The emission spectrum of the fluorescent glass, as tested using a blue LED excitation source, is as follows: Figure 1 The light is mainly distributed in the 500–700 nm range, and no ultraviolet or blue light leakage below 500 nm was detected in the spectrum, verifying that it has high spectral purity.

[0029] The CIE 1931 chromaticity diagram of the fluorescent glass in this embodiment is shown in Figure 2, exhibiting a yellow light output characteristic.

[0030] Comparative Example 1: This comparative example is the same as Example 1, except that the formulation and additives are prepared as follows: The composition of the glass matrix, by molar percentage, is: SiO2 55 mol%, B2O3 20 mol%, P2O5 10 mol%, Bi2O3 5 mol%, ZnO 5 mol%, Al2O3 5 mol%. The total amount of the glass matrix added is 89.7%.

[0031] Rare earth phosphor: Ce 3+ Lu3Al5O doped 12 Phosphor and Eu 3+ The total amount of CaAlSiN3 phosphor added was 10 wt%.

[0032] Functional additives: No rare earth oxide absorbents (CeO2, Y2O3, etc. are added at 0 wt%), only nano-SiO2 at 0.3 wt%.

[0033] The preparation method is the same as in Example 1: ball milling dispersion, drying and powder collection; graphite mold installation and coating with boron nitride isolation layer; SPS pre-pressed under vacuum at 10 MPa, heated to 500 ℃ and held for 8 min; annealed at 450 ℃ for 15 min, and then double-sided grinding and polishing to a thickness of 0.5 mm.

[0034] Comparative Example 2: This comparative example is the same as Example 1, except that the formulation and additives are prepared as follows: The composition of the glass matrix, by molar percentage, is: SiO2 55 mol%, B2O3 20 mol%, P2O5 10 mol%, Bi2O3 5 mol%, ZnO 4 mol%, Al2O3 5 mol%, SnF2 1 mol%. The total amount of the glass matrix added is 89.7%.

[0035] Rare earth phosphors: only Eu is added 3+ The phosphor was doped with CaAlSiN3 at an amount of 10 wt%.

[0036] Functional additives: No rare earth oxide absorbents (CeO2, Y2O3, etc. are added at 0 wt%), only nano-SiO2 at 0.3 wt%.

[0037] The preparation method is the same as in Example 1: ball milling dispersion, drying and powder collection; graphite mold installation and coating with boron nitride isolation layer; SPS pre-pressed under vacuum at 10 MPa, heated to 500 ℃ and held for 8 min; annealed at 450 ℃ for 15 min, and then double-sided grinding and polishing to a thickness of 0.5 mm.

[0038] like Figure 3As shown, Example 1 showed no leakage in the ultraviolet and yellow light ranges. In contrast, Comparative Examples 1 and 2 both exhibited identifiable emission peaks in the 488–492 nm range, with significant pump and short-wavelength residues, failing to completely isolate blue light.

Claims

1. A rare-earth-doped fluorescent glass for special yellow light illumination, comprising a glass matrix, rare-earth phosphors dispersed within the glass matrix, and functional additives; characterized in that: The functional additives include rare earth oxides and scattering particles, wherein the rare earth oxides are one or more of CeO2, Y2O3, Gd2O3, Nd2O3, and Eu2O3, and the scattering particles are one or more of SiO2, Al2O3, ZrO2, TiO2, and VO2. The mass percentages of the glass matrix, rare earth phosphor, and functional additives are 70–90 wt%, 8–28 wt%, and 0.5–2 wt%, respectively.

2. The rare-earth-doped fluorescent glass for special yellow light illumination according to claim 1, characterized in that, The glass matrix comprises, by molar percentage, 50-60 mol% SiO2, 15-25 mol% B2O3, 5-12 mol% P2O5, 3-7 mol% Bi2-O3, 2-5 mol% ZnO, 2-4 mol% Al2O3, and 0.5-2 mol% SnF2.

3. The rare-earth-doped fluorescent glass for special yellow light illumination according to claim 1, characterized in that, The rare earth ion of the rare earth phosphor is La. 3+ Ce 3+ Eu 3+ 、Tb 3+ Gd 3+ 、Sm 3+ Pr 3+ At least one of them.

4. A rare-earth-doped fluorescent glass for special yellow light illumination according to claim 1, characterized in that, The scattering particles have a diameter of 50–300 nm.

5. The rare-earth-doped fluorescent glass for special yellow light illumination according to claim 1, characterized in that, The fluorescent glass can absorb ultraviolet and blue light with wavelengths of 200nm to 500nm and emit light with wavelengths of 500nm to 700nm.

6. A method for preparing the rare-earth-doped fluorescent glass according to any one of claims 1-5, characterized in that, Includes the following steps: S1: Mix glass matrix powder, rare earth phosphor, rare earth oxide and scattering particles, add dispersant and solvent, disperse by ball milling and dry to obtain dry powder or slurry; S2: The dry powder or slurry is loaded into a graphite or metal mold, and the inner wall of the mold is coated with a boron nitride or graphite paper isolation layer; S3: Densification is carried out in a spark plasma sintering apparatus by applying pulsed current and pressure of 20–60 MPa at 380–580 °C, and then cooling in a vacuum or inert atmosphere. S4: The resulting dense body is annealed at 200–500 °C and then ground and polished to obtain rare earth-doped fluorescent glass.

7. The preparation method according to claim 6, characterized in that, The dispersant in step S1 is at least one of polyvinylpyrrolidone, polycarboxylate, polyacrylate, or sodium dodecyl sulfate, and the solvent is at least one of ethanol, isopropanol, propylene glycol methyl ether, or N-methylpyrrolidone.

8. The preparation method according to claim 6, characterized in that, In step S3, the heating rate is controlled at 5–50 ℃ / min, and the holding time is controlled at 2–15 min.

9. The application of the rare earth ion fluorescent glass according to any one of claims 1-5 or the preparation method according to any one of claims 6-8 in optical materials.

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